Photophysical properties of acetylene-linked syn bimane oligomers: a molecular photonic wire.

Computational studies using correlated wave function methods and density functional theory were carried out on a series of acetylene-linked bimane oligomers with particular emphasis on their excitonic properties and implications for intra-chain excitation energy transfer (EET). The low energy barriers found for the rotation of bimane subunits about the longitudinal axis are such that the π-conjugation is easily disrupted. Nevertheless, a distinctive feature of the oligomer lies in the parallel alignment of the S1 transition dipole along the longitudinal axis, which sustains electronic coupling between adjacent bimane subunits over a range of torsional angles and is crucial for driving intra-chain EET. Using a model that comprises hexameric donor and acceptor fragments, we evaluated electronic couplings and spectral overlaps, and applied Fermi's golden rule (in the weak electronic coupling regime) to approximate the lower limit of intra-chain EET in an acetylene-linked bimane photonic wire.

Using non-empirically tuned range-separated functionals with simulated emission bands to model fluorescence lifetimes.

Fluorescence lifetimes were evaluated using TD-DFT under different approximations for the emitting molecule and various exchange-correlation functionals, such as B3LYP, BMK, CAM-B3LYP, LC-BLYP, M06, M06-2X, M11, PBE0, ωB97, ωB97X, LC-BLYP*, and ωB97X* where the range-separation parameters in the last two functionals were tuned in a non-empirical fashion. Changes in the optimised molecular geometries between the ground and electronically excited states were found to affect the quality of the calculated lifetimes significantly, while the inclusion of vibronic features led to further improvements over the assumption of a vertical electronic transition. The LC-BLYP* functional was found to return the most accurate fluorescence lifetimes with unsigned errors that are mostly within 1.5 ns of experimental values.

Rapid intersystem crossings in anti bimanes.

We have carried out first principles electronic structure calculations on the ground and excited valence states of syn and anti bimanes. While syn bimanes fluoresce strongly after photoexcitation to the first excited singlet state (S1) and are commonly used as fluorophores in biological labeling studies, anti bimanes largely phosphoresce at low temperatures. We show that this is due to subtle differences in the energetic ordering of excited singlet and triplet states within the isomers. In particular, T2 in anti bimanes is characterized by a π→π* transition and large exchange interactions with the singlet counterpart cause it to lie below and energetically close to S1 at the Franck-Condon region. This opens up a pathway for very fast intersystem crossing (ca. 10(11) s(-1)) from the optically bright S1 state to the triplet manifold, which effectively quenches fluorescence. On the other hand, T2 is energetically inaccessible to S1 in syn bimanes and intersystem crossing via S1→ T1 cannot compete effectively with fluorescence to S0. We have also located minimum energy conical intersections between S0 and S1 in bimanes. However, these structures are significantly distorted from their equilibrium geometries as well as energetically much higher than S1 at the Franck-Condon region. They are therefore not expected to play a part in the photophysics of bimanes after excitation to S1.

Factor XII promotes blood coagulation independent of factor XI in the presence of long-chain polyphosphates.

BACKGROUND: Inorganic polyphosphates (polyP), which are secreted by activated platelets (short-chain polyP) and accumulate in some bacteria (long-chain polyP), support the contact activation of factor XII (FXII) and accelerate the activation of FXI. OBJECTIVES: The aim of the present study was to evaluate the role of FXI in polyP-mediated coagulation activation and experimental thrombus formation. METHODS AND RESULTS: Pretreatment of plasma with antibodies that selectively inhibit FXI activation by activated FXII (FXIIa) or FIX) activation by activated FXI (FXIa) were not able to inhibit the procoagulant effect of long or short-chain polyP in plasma. In contrast, the FXIIa inhibitor, corn trypsin inhibitor, blocked the procoagulant effect of long and short polyP in plasma. In a purified system, long polyP significantly enhanced the rate of FXII and prekallikrein activation and the activation of FXI by thrombin but not by FXIIa. In FXI-deficient plasma, long polyP promoted clotting of plasma in an FIX-dependent manner. In a purified system, the activation of FXII and prekallikrein by long polyP promoted FIX activation and prothombin activation. In an ex vivo model of occlusive thrombus formation, inhibition of FXIIa with corn trypsin inhibitor but not of FXI with a neutralizing antibodies abolished the prothrombotic effect of long polyP. CONCLUSIONS: We propose that long polyP promotes FXII-mediated blood coagulation bypassing FXI. Accordingly, some polyp-containing pathogens may have evolved strategies to exploit polyP-initiated FXII activation for virulence, and selective inhibition of FXII may improve the host response to pathogens.